Knitted/woven fabric of polyester fiber

ABSTRACT

A knitted/woven fabric of polyester fibers is produced from a polyester polymer obtained by condensation-polymerizing an aromatic dicarboxylate in the presence of a catalyst which comprises a mixture of a titanium compound ingredient (A) comprising a titanium alkoxide and at least one product of the reaction of the titanium alkoxide with a specific carboxylic acid or anhydride thereof and a specific phosphorus compound ingredient (B) and/or comprises a product of the reaction of a titanium compound ingredient (C) with a specific phosphorus compound ingredient (D). The knitted/woven fabric obtained has a satisfactory color tone (low value of b*) and is excellent in suitability for knitting/weaving and dyeability.

TECHNICAL FIELD

The present invention relates to a polyester fiber knitted or wovenfabric. More particularly, the present invention relates to a polyesterfiber knitted or woven fabric formed from a polyester resin having agood color tone and an excellent formability.

BACKGROUND ART

It is well known that polyester resins, particularly polyethyleneterephthalate, polyethylene naphthalate, polytrimethylene terephthalateand polytetramethylene terephthalate have excellent mechanical, physicaland chemical properties, and thus are widely utilized for fibers, filmsand other shaped articles and, particularly, for knitted and wovenfabrics, the polyester resin products have excellent mechanicalstrength, dimensional stability, heat resistance and light resistance.

Each of the above-mentioned polymers for fibers, for examplepolyethylene terephthalate, is usually produced by, for example,preparing a ethylene glocol ester of terephthalic acid and/or anoligomer thereof, and then polycondensation-reacting the ester monomeror oligomer in the presence of a polycondensation catalyst under areduced pressure while heating the reaction system until a desireddegree of polymerization of the resultant polyester resin is attained.Other polyesters can be produced by procedures similar to theabove-mentioned procedures.

With respect to the procedures, it is well known that the quality of theresultant polyester resin is greatly influenced by the type of thepolycondensation catalyst and, as a polycondensation catalyst forpolyethylene terephthalate, antimony compounds are most widely employed.

However, when an antimony compound is used as the polycondensationcatalyst, there arises the following problem. That is, when theresulting polyester is continuously melt-spun for a long time, around aspinneret for melt spinning, foreign matter (hereinafter sometimesmerely referred to as spinneret foreign matter) is deposited thereby tocause a bending phenomenon of a molten polymer stream extruded throughthe spinneret, which leads to the occurrence of fuzz and/or breakage offiber yarns obtained in the spinning step and/or the drawing step.Particularly, in the production of filaments (of which the performancesmust be utilized to the maximum extent), the above-mentioned problemmust be solved.

To solve the problem, it is known to use a titanium compound, forexample, titanium tetrabutoxide as a polycondensation catalyst. In thiscase, however, the resultant polyester polymer exhibits a low thermalstability and, when melted, the polymer is significantly deteriorated.Therefore the production of the polyester filaments having highmechanical strength is difficult. Also, there arises a problem that theresultant polyester polymer is colored yellow, and the finally resultantfibers exhibit an unsatisfactory color tone.

As means for solving the problem, it is disclosed in, for example,Japanese Examined Patent Publication No. 59-46258, that a productobtained by reacting a titanium compound with trimellitic acid is usedas a catalyst for preparation of a polyester, and in, for example,Japanese Unexamined Patent Publication No. 58-38722, that a productobtained by reacting a titanium compound with a phosphite ester is usedas a catalyst for producing a polyester. Although the thermal stabilityof the melt of the polyester is certainly improved to some extent bythis processes, the degree of improvement is insufficient and theresulting polyesters have insufficient color tone. Therefore, a furtherimprovement in the color tone of the polyester is required.

Furthermore, Japanese Unexamined Patent Publication (Kokai) No. 7-138354proposes use of a complex of a titanium compound with a phosphoruscompound as a catalyst for the preparation of a polyester. Although thethermal stability of the melt of the polyester is certainly improved tosome extent by this process, the degree of improvement is stillinsufficient and the color tone of the resulting polyester must befurther improved.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a polyester fiberknitted or woven fabric formed from polyester fibers having a good colortone (a high L* value and a low b* value) and a high quality.

The polyester fiber knitted or woven fabric of the present invention isone formed from yarns comprises polyester fibers comprising, as aprincipal component, a polyester polymer which has been produced bypolycondensing an aromatic dicarboxylate ester in the presence of acatalyst,

-   -   wherein    -   the catalyst comprises at least one member selected from        mixtures (1) and reaction products (2);    -   (1) the mixtures (1) for the catalyst comprise a titanium        compound component (A) mixed with phosphorus compound component        (B),    -   in which mixtures (1),    -   the component (A) comprises at least one member selected from        the group consisting of (a) titanium alkoxides represented by        the general formula (I):        in which formula (I), R¹, R², R³ and R⁴ respectively and        independently from each other represent a member selected from        alkyl groups having 1 to 20 carbon atoms and a phenyl group, m        represent an integer of 1 to 4, and when m represents an integer        of 2, 3 or 4, the 2, 3 or 4 R²s and R³s may be respectively the        same as each other or different from each other, and (b)        reaction products of the titanium compounds of the general        formula (I) with aromatic polycarboxylic acids represented by        the formula (II):        in which formula (II), n represents an integer of 2 to 4, or        anhydrides of the acids of the formula (II); and the        component (B) comprising at least one phosphorus compound        represented by the general formula (III):        in which formula (III), R⁵, R⁶ and R⁷ respectively and        independently from each other represent an alkyl group having 1        to 4 carbon atoms, X represents a member selected from a —CH₂—        group and a —CH(Y)— group (wherein Y represents a phenyl group),    -   the mixture (1) for the catalyst for the polycondensation being        employed in an amount satisfying the requirements represented by        the following expressions of relation (i) and (ii):        1≦M _(p) /M _(Ti)≦15  (i)        and        10≦M _(p) +M _(Ti)≦100  (ii)        wherein M_(Ti) represents a ratio in % of a value in milli mole        of titanium element contained in the titanium compound        component (A) to a value in mole of the aromatic dicarboxylate        ester, and M_(p) represents a ratio in % of a value in milli        mole of phosphorus element contained in the phosphorus compound        component (A) to the value in mole of the aromatic dicarboxylate        ester,    -   (2) the reaction products (2) for the catalyst comprises a        component (C) reacted with a component (D),    -   in which reaction products (2),    -   the component (C) comprises at least one member selected from        the group consisting of (C) titanium alkoxides represented by        the general formula (IV):        in which formula (IV), R⁸, R⁹, R¹⁰ and R¹¹ respectively and        independently from each other represents an alkyl group having 1        to 20 carbon atoms, p represents an integer of 1 to 3, and when        p represents an integer of 2 or 3, 2 or 3 R⁹s and R¹⁰s may be        respectively the same as each other or different from each        other, and (d) reaction products of the titanium alkoxides of        the general formula (IV) with aromatic polycarboxylic acids        represented by the above-mentioned general formula (II) or        anhydrode of the acids; and    -   the component (D) comprises at least one phosphorus compound        represented by the general formula (V):        in which formula (V), R¹² represents an alkyl group having 1 to        20 carbon atoms or an aryl group having 6 to 20 carbon atoms,        and q represents an integer of 1 or 2.

In the polyester fiber knitted or woven fabric of the present invention,and preferably in each of the component (A) of the mixture (1) and thecomponent (C) of the reaction products (2) for the catalyst, a reactionmolar ratio of each of titanium alkoxides (a) and (c) to the aromaticpolycarboxylic acid of the general formula (II) or the anhydride thereofis in the range of from 2:1 to 2:5.

In the polyester fiber knitted or woven fabric of the present invention,and preferably in the reaction product (2) for the catalyst, a reactionamount ratio of the component (D) to the component (C) is in the rangeof, in terms of ratio (P/Ti) of the molar amount of phosphorus atomscontained in the component (D) to the molar amount of titanium atomscontained in the component (C), from 1:1 to 3:1.

In the polyester fiber knitted or woven fabric of the present invention,the phosphorus compound of the general formula (V) for the reactionproduct (2) is preferably selected from monoalkyl phosphates.

In the polyester fiber knitted or woven fabric of the present invention,the dialkyl aromatic dicarboxylate ester is preferably produced by atransesterification reaction of a dialkyl ester of an aromaticdicarboxylic acid with an alkylene glycol.

In the polyester fiber knitted or woven fabric of the present invention,the aromatic dicarboxylic acid is preferably selected from terephthalicacid, 1,2-naphthalene dicarboxylic acid, phthalic acid, isophthalicacid, diphenyldicarboxylic acid and diphenoxyethane dicarboxylic acidand the alkylene glycol is preferably selected from ethylene glycol,butylene glycol, trimethylene glycol, propylene glycol, neopentylglycol, hexamethylene glycol and dodecamethylene glycol.

In the polyester fiber knitted or woven fabric of the present invention,the polyester polymer preferably has an L* value of 77 to 85 and a b*value of 2 to 5, determined in accordance with the L*a*b* colorspecification of JIS Z 8729.

BEST MODE FOR CARRYING OUT THE INVENTION

The polyester fiber knitted or woven fabric of the present invention isformed from polyester fibers comprising, as a principal component, apolyester polymer.

The polyester polymer is one prepared by polycondensing an aromaticdicarboxylate ester in the presence of a catalyst. The polycondensationcatalyst comprises at least one member selected from mixtures (1) of atitanium compound component (A) with a phosphorous compound component(B) as specified below and reaction products of a titanium compoundcomponent (C) and a phosphorus compound component (D) as specifiedbelow.

The titanium compound component (A) for the mixture (1) for thepolycondensation catalyst comprises at least one member selected fromthe group consisting of:

-   -   (a) titanium alkoxides represented by the general formula (I):        in which formula (I), R¹, R², R³ and R⁴ respectively and        independently from each other represent a member selected from        alkyl groups having 1 to 20 carbon atoms, preferably 1 to 6        carbon atoms, and a phenyl group, m represents an integer of 1        to 4, preferably 2 to 4, and when m represents an integer of 2,        3 or 4, the 2, 3 or 4 R²s and R³s may be respectively the same        as each other or different from each other, and    -   (b) reaction products of the titanium compounds of the general        formula (I) with aromatic polycarboxylic acids represented by        the general formula (II):        in which formula (II), n represents an integer of 2 to 4,        preferably 3 or 4, or anhydrides of the acids of the formula        (II).

The phosphorous compound component (B) for the mixture (1) for thepolycondensation catalyst comprises at least one compound represented bythe general formula (III):

in which formula (III), R⁵, R⁶ and R⁷ respectively and independentlyfrom each other represent an alkyl group having 1 to 4 carbon atoms, Xrepresents a member selected from a —CH₂— group and a —CH(Y)— group(wherein Y represents a phenyl group).

Also, the titanium compound component (C) for the reaction products (2)for the polycondensation catalyst comprises at least one member selectedfrom the group consisting of:

-   -   (c) titanium alkoxides represented by the general formula (IV):        in which formula (IV), R⁸, R⁹, R¹⁰ and R¹¹ respectively and        independently from each other represents an alkyl group having 1        to 20 carbon atoms, and preferably 1 to 6 carbon atoms, p        represents an integer of 1 to 3, and preferably 1 to 2, and when        p represents an integer of 2 or 3, 2 or 3 R⁹s and R¹⁰s may be        respectively the same as each other or different from each        other, and    -   (d) reaction products of the titanium alkoxides of the general        formula (IV) with aromatic polycarboxylic acids represented by        the above-mentioned general formula (II) or anhydrode of the        acids.

The phosphorus compound component (D) for the reaction products (2) forthe polycondensation catalyst comprises at least one compoundrepresented by the general formula (V):

in which formula (V), R¹² represents an alkyl group having 1 to 20carbon atoms or an aryl group having 6 to 20 carbon atoms, and qrepresents an integer of 1 or 2.

In the case where mixtures (1) of a titanium compound component (A) witha phosphorous compound component (B), or reaction products of a titaniumcompound component (C) with a phosphorous compound component (D) areemployed, as polycondensation catalysts, the titanium alkoxide (a) or(c) represented by the general formula (I) or (IV) and usable for thetitanium compound component (A) or (C), and the reaction product (b) or(d) of titanium alkoxide (a) or (c) with an aromatic polycarboxylic acidrepresented by the general formula (II) or with an anhydride thereof,have a high solubility in or a high affinity to the polyester polymer,and thus the catalyst comprising the mixture (1) or reaction product (2)exhibits a high solubility in or a high affinity to the polyesterpolymer, which is sufficient in practice. Therefore, even if the mixture(1) or reaction product (2) for the catalyst remains in the polyesterpolymer produced by the polycondensation procedure, and the polyesterpolymer is melt-spun, no foreign matter is accumulated around thespinneret for melt spinning, and thus polyester filaments having a highquality can be produced with high melt-spinning efficiency.

The titanium alkoxide (a) of the general formula (I) usable for thetitanium compound component (A) for the polycondensation catalyst ispreferably selected from titanium tetraisoproxide, titaniumtetraproxide, titanium tetra-n-butoxide, titanium tetraethoxide,titanium tetraphenoxide, octaalkyl trititanates and hexaalkyldititanates.

The titanium alkoxide (C) of the general formula (IV) usable for thetitanium compound component (C) for the polycondensation catalyst ispreferably selected from titanium tetraalkoxides, for example, titaniumtetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, andtitanium tetraethoxide; and alkyl titanates, for example, octaalkyltrititanates and hexaalkyl dititonates. Particularly, titaniumtetrabutoxide, which has a high reactivity with the phosphorus compoundcomponent, is preferably used.

The aromatic polycarboxylic acids of the general formula (II) and theanhydrides thereof, to be reacted with the titanium alkoxides (a) or (c)are preferably selected from phthalic acid, trimellitic acid,hemimellitic acid, pyromellitic acid and anhydrides of theabove-mentioned acids. Particularly, when trimellitic anhydride is used,the resultant reaction product (b) exhibits a high affinity to thepolyester polymer and thus contributes to preventing the accumulation ofthe foreign matter.

To react the titanium alkoxide (a) or (c) with the aromaticpolycarboxylic acid of the general formula (II) or the anhydridethereof, preferably, the aromatic polycarboxylic acid or the anhydridethereof is dissolved in, for example, a solvent; to the resultant mixedliquid, a titanium alkoxide (a) or (c) is added dropwise; and themixture is heated at a temperature of 0 to 200° C. for at least 30minutes. The above-mentioned solvent is optionally selected from ethylalcohol, ethyleneglycol, trimethyleneglycol, tetramethyleneglycol,benzene and xylene.

There is no limitation to the molar ratio for the reaction of thetitanium alkoxide (a) or (c) to the aromatic polycarboxylic acid of thegeneral formula (II) or the anhydride thereof. However, if theproportion of the titanium alkoxide is too high, the resultant polyesterpolymer may have a degraded color tone and/or too low a softening point.On the contrary, if the proportion of the titanium alkoxide is too low,the reaction rate of the polycondensation may decrease. Accordingly, thereaction molar ratio of the titanium alkoxide (a) or (c) to the aromaticpolycarboxylic acid of the general formula (II) or the anhydric thereofis preferably in the range of from (2:1) to (2:5).

The reaction product (b) or (d) produced by the above-mentioned reactionmay be employed without refining or after refining by recrystallizationthereof by using acetone, methyl alcohol and/or ethyl acetate.

In the present invention, the phosphorus compound (phosphonatecompounds) of the general formula (III) usable for the phosphoruscompound component (B) for the mixture (1) for the polycondensationcatalyst is preferably selected from esters of phosphonic acidderivatives, for example, dimethyl esters, diethyl esters, dipropylesters and dibutyl esters of phosphonic acid derivatives, for example,carbomethoxymethanephosphonic acid, carboethoxymethanephosphonic acid,carbopropoxymethanephosphonic acid, carbobutoxymethanephosphonic acid,carboxyphenylmethanephosphonic acid, carboethoxyphenylmethanephosphonicacid, carbopropoxyphenylmethanephosphonic acid, andcarbobutoxyphenylmethanephosphonic acid.

When the phosphorus compound component (B) comprising the phosphoruscomponent (phosphonate compound) of the general formula (III) isemployed for the polycondensation reaction of the aromatic dicarboxylateester, the reaction thereof with the titanium compound component (A) canproceed at a relatively slow reaction rate compared with a conventionalphosphorus compound which is usually used as a conventional stabilizerand, thus, during the polycondensation procedure, the catalytic activityof the titanium compound component (A) can be maintained high for a longtime. Therefore, as a result, the amount ratio of the titanium compoundcomponent (A) to the aromatic dicarboxylate ester in thepolycondensation system can be made low. Also, even if thepolycondensation system containing the phosphorus compound component (B)comprising the phosphorus compound of the general formula (III) is addedwith a large amount of a stabilizer, the thermal stability of theresultant polyester polymer is not decreased and the color tone of thepolyester polymer is not affected.

In the present invention, in the case where the mixture (1) is employedfor the polycondensation catalyst, the mixture (1) is employed in anamount satisfying the requirements represented by the followingexpressions of relation (i) and (ii):1≦M _(p) /M _(Ti)≦15  (i)and10≦M _(p) +M _(Ti)≦100  (ii)wherein M_(Ti) represents a ratio in % of a value in milli mole oftitanium element contained in the titanium compound component (A) to avalue in mole of the aromatic dicarboxylate ester, and M_(p) representsa ratio in % of a value in milli mole of phosphorus element contained inthe phosphorus compound component (A) to the value in mole of thearomatic dicarboxylate ester.

The ratio M_(p)/M_(Ti) is 1 or more but not more than 15, preferably 2or more but not more than 10. If the ratio M_(p)/M_(Ti) is less than 1,the resultant polyester polymer may have a yellowish color tone, and ifthe ratio is more than 15, the resultant polycondensation catalyst mayexhibit an insufficient proportion effect on the polycondensationreaction, and thus the target polyester polymer may be difficult toproduce. The range of the ratio M_(p)/M_(Ti) usable for the presentinvention is narrower than that of the conventional Ti—P catalystsystem. By establishing the ratio M_(p)/M_(Ti) in the above-mentionedrange, an excellent catalytic effect, which has not been obtained in theconventional Ti—P catalyst system, can be obtained.

The sum of (M_(Ti)+M_(p)) is 10 or more but not more than 100,preferably 20 or more but not more than 70. If the sum of (M_(Ti)+M_(p))is less than 10, the resultant polyester polymer exhibits aninsufficient fiber-forming property, the production efficiency in themelt-spinning procedure is insufficient, and the resultant fibersexhibit an unsatisfactory performances. Also, if the sum of(M_(Ti)+M_(p)) is more than 100, and when the resultant polyesterpolymer is melt-spun, foreign matter is accumulated in a small amountaround the spinneret. Generally, the M_(Ti) value is preferably 2 to 15%and more preferably 3 to 10%.

In the case where the reaction products (2) are used as apolycondensation catalyst for the present invention, the phosphoruscompounds of the general formula (V) for the phosphorus compoundcomponent (D) include, for example, monoalkyl phosphates, for example,mono-n-butyl phosphate, monohexyl phosphate, monododecyl phosphate,monolauryl phosphate, monooleyl phosphate, etc.; monoaryl phosphates,for example, monophenyl phosphate, monobenzyl phosphate,mono(4-ethylphenyl) phosphate, monobiphenyl phosphate, mononaphthylphosphate, monoanthoryl phosphate, etc.; dialkyl phosphates, forexample, diethyl phosphate, dipropyl phosphate, dibutyl phosphate,dilauryl phosphate, dioleyl phosphate, etc; and diaryl phosphates, forexample, diphenyl phosphate, etc. Among these phosphate compounds, themonoalkyl phosphates or monoaryl phosphates of the formula (V) in whichq is one, are preferably employed.

The phosphorus compound component (D) usable for the present inventionmay consist of a mixture of two or more phosphorus compounds of thegeneral formula (V). For example, a mixture of a monoalkyl phosphatewith a dialkyl phosphate and a mixture of a monophenyl phosphate with adiphenyl phosphate are preferably employed. Particularly, in themixture, a monoalkyl phosphate is preferably contained in an amount of50% by mass or more, more preferably 90% by mass or more, based on thetotal mass of the mixture.

The reaction products of the titanium compound component (C) with thephosphorus compound component (D) can be produced by, for example,mixing the components (C) and (D) with each other and heating theresultant mixture in glycol. Namely, when a glycol solution containingthe titanium compound component (C) and the phosphorus compoundcomponent (D) is heated, the glycol solution becomes cloudy white andthe reaction product of the components (C) and (D) with each other isprecipitated as a precipitate. The precipitate is collected and used asa catalyst for the production of the polyester polymer. In theproduction of the reaction product (2) for the catalyst, the glycol tobe used is preferably the same as that used as a glycol component forthe polyester polymer to be produced by using the resultant catalyst.For example, in the case where the target polyester polymer ispolyethylene terephthalate polymer, ethylene glycol is used, in the caseof polytrimethylene terephthalate polymer, 1,3-propanediol is used, andin the case of polytetramethylene terephthalate polymer,tetramethyleneglycol is used.

The reaction product (2) for the polycondensation catalyst for thepresent invention can be produced by mixing the titanium compoundcomponent (C), the phosphorus compound component (D) and glycolaltogether and heating the mixture. In this method, however, when themixture is heated, a reaction product, insoluble in glycol, is producedby the reaction of the titanium compound component (C) with thephosphorus compound component (D) and precipitate in the reactionsystem. Therefore, the reaction procedure until the precipitation ispreferably carried out uniformly. Accordingly, to produce the reactionproduct precipitate with a high efficiency, preferably a solution of thetitanium compound components in glycol and a solution of the phosphoruscompound component (D) are separately prepared, and these solutions aremixed together and heated.

The reaction temperature of the components (C) and (D) is preferably inthe range of from 50° C. to 200° C., and the reaction time is preferablyone minute to 4 hours. If the reaction temperature is too low, thereaction may be incompletely effected or a very long reaction time isneeded, and thus the target reaction product precipitate may not beobtained by a uniform reaction with a high efficiency.

The phosphorus compound component (D) and the titanium compoundcomponent (C) are preferably subjected, in a ratio, in terms of molarratio of phosphorus atoms to titanium atoms, of 1.0 to 3.0, morepreferably 1.5 to 2.5, to the heat-reaction. When the components (D) and(C) are employed in the above-mentioned ratio, the phosphorus compoundcomponent (D) can be substantially completely reacted with the titaniumcompound component (C), and substantially no incompletely reactedproduct is present in the reaction product. Therefore, the resultantreaction product can be used for the catalyst without refining, and theresultant polyester polymer has a good color tone. Also, as the reactionproduct contains substantially no unreacted phosphorus compound of theformula (V), the polycondensation reaction for the production of thepolyester can be conducted with a high productivity and withoutobstruction due to the non-reacted phosphorus compound.

The reaction product (2) for the polycondensation catalyst usable forthe present invention preferably contains the compound represented bythe general formula (VI):

In the formula (VI), R¹³ and R¹⁴ respectively and independently fromeach other represent a member selected from alkyl groups having 1 to 10carbon atoms and derived from the R⁸, R⁹, R¹⁰ and R¹¹ groups in thegeneral formula (IV) which represents the titanium alkoxide for thetitanium compound component (C) and R¹² in the general formula (V) whichrepresents the phosphorus compound for the phosphorus compound component(D), or aryl groups having 6 to 12 carbon atoms and derived from the R¹²group of the phosphorus compound of the formula (V).

The reaction product of the titanium compound with the phosphorouscompound of the formula (V), represented by the formula (VI), has a highcatalytic activity and the polyester polymer produced by using thisreaction product exhibits a good color tone (a low b* value), andcontains acetaldehyde, residual metals and cyclic trimers insufficiently low amounts in practice and has practically satisfactorypolymer properties. The reaction product represented by the formula (IV)is preferably contained in a content of 50% by mass or more, morepreferably 70% by mass or more, in the polycondensation catalyst.

In the polycondensation of the aromatic dicarboxylate ester in thepresence of the above-mentioned reaction product (2), the precipitate ofthe reaction product (2) suspended in glycol can be employed as acatalyst without separating the precipitate from glycol. Alternately,the reaction product precipitate is separated from the suspensionthereof in glycol by a centrifugal precipitation treatment or afiltration treatment, the separated reaction product is refined by arecystallization treatment in a recrystallizing agent, for example,acetone, methyl alcohol and/or water, then the refined product isemployed as a poly-condensation catalyst. The chemical structure of thereaction product (2) for the polycondensation catalyst can be confirmedby a metal quantitative determination according to solid NMR and XMA.

The polyester polymer usable for the present invention is produced by apolycondensation of an aromatic dicarboxylate ester in the presence of acatalyst comprising a mixture (1) of the titanium compound component (A)with the phosphorus compound (phosphonate compound) component (B) and/ora reaction product (2) of the titanium compound component (C) with thephosphorus compound component (D). In the present invention, thearomatic dicarboxylate ester is preferably a diester of an aromaticdicarboxylic acid component with an aliphatic glycol component.

The aromatic dicarboxylic acid component preferably comprises, as aprincipal component, terephthalic acid. More particularly, theterephthalic acid is contained in a content of 70 molar % or more on thebasis of the total content of the aromatic dicarboxylic acid component.The preferable aromatic discarboxylic acids other than terephthalic acidfor the present invention include, for example, phthalic acid,isophthalic acid, naphthalene dicarboxylic acid, diphenylldicarboxylicacid and diphenoxyethane dicarboxylic acid.

The aliphatic glycol component preferably comprises an alkylene glycol,for example, ethylene glycol, trimethylene glycol, propylene glycol,tetramethylene glycol, neopentyl glycol, hexamethylene glycol,dodecamethylene glycol, etc. Among them, ethylene glycol is morepreferably employed. In the present invention, the polyester polymer ispreferably selected from polyester polymers having, as principalrepeating units, ethylene terephthalate groups formed from terephthalicacid and ethylene glycol. In this case, the repeating ethyleneterephthalate units are preferably contained in a content of 70 molar %or more based on the total molar amount of the repeating units.

The polyester polymer usable for the present invention may be selectedfrom copolyester polymers containing comonomer components, as acidcomponents or diol components, capable of forming the polyesterstructure.

The carboxylic acid components for the copolyester include difunctionalcarboxylic acids, such as the above-mentioned aromatic dicarboxylicacids aliphatic dicarboxylic acids, for example, adipic acid, sebasicacid, azelaic acid and decanedicarboxylic acid, and cycloaliphaticdicarboxylic acids, for example, cyclohexanedicarboxylic acid, andester-forming derivatives of the difunctional carboxylic acids. Also,the diol components for the copolyester include the above-mentionedaliphatic diols, cycloaliphatic glycol compounds, for example,cyclohexane diol, and aromatic diol compounds, for example, bisphenol,hydroquinone, and 2,2-bis(4-β-hydroxyethoxyphenyl) propane.

Further, copolyester polymers produced by copolymerizing acopolymerization component comprising polyfunctional compounds, forexample, trimesic acid, trimethylolethane, trimethylolpropane,trimethylolmethane and pentaerythriol, can be used for the presentinvention.

In the present invention, the homopolyester polymers and the copolyesterpolymers may be employed alone or in a mixture of two or more thereof.

For the polyester polymer for the polyester fiber fabric of the presentinvention, polycondensation products of aromatic dicarboxylate esterproduced from the above-mentioned aromatic dicarboxylic acid andaliphatic glycol are preferably used. The aromatic dicarboxylate estercan be produced by a diesterification reaction of the aromaticdicarboxylic acid with the aliphatic glycol, or by a transesterificationreaction of a dialkylester of the aromatic dicarboxylic acid with analiphatic glycol. The production of the polyester polymer through thetransesterification reaction using, as a starting compound, the dialkylester of the aromatic dicarboxylate, is advantageous in that thepolycondensation procedure can be carried out with less scattering ofthe phosphorus compound added as a phosphorus stabilizing agent to thepolycondensation system in comparison with the polycondensationprocedure of the aromatic dicarboxylate ester produced by thediesterification reaction of the aromatic dicarboxylic acid.

Further, preferably a portion or all of the titanium compound component(A) or (C) is mixed with the reaction system before the start of thetransesterification reaction, to utilize the titanium compound component(A) or (C) as a catalyst for both the transesterification andpolycondensation reactions. In this utilization of the titanium compoundcomponent (A) or (C), the final content of the titanium compoundcomponent in the polyester polymer can be reduced. Particularly, in theproduction of, for example, polyethylene terephthalate, thetransesterification reaction of a dialkyl ester, of an aromaticdicarboxylic acid component including, as a principal component,terephthalic acid, with ethylene glycol is preferably carried out in thepresence of the titanium compound component (A) comprising at least onemember selected from the group consisting of titanium alkoxides (a)represented by the general formula (I), and reaction products (b)produced by a reaction of the titanium alkoxides represented by thegeneral formula (I) with an aromatic polycarboxylic acids represented bythe general formula (II) or anhydrides thereof. Then, the reactionmixture produced by the transesterification reaction and containing thediester of the aromatic dicarboxylic acid with ethylene glycol is addedwith a phosphorous compound (phosphate component) component (B)represented by the general formula (III), or with a reaction product ofthe titanium compound component (C) with the phosphorous compoundcomponent (D), to proceed the polycondensation reaction of the aromaticdicarboyxlate ester.

Usually the transesterification reaction is carried out under theambient atmospheric pressure. When the reaction is carried out under apressure of 0.05 to 0.20 MPa, a transesterification reaction due to thecalystic activity of the titanium compound component (A) is furtherpromoted, and there does not occur the generation of a by-product,consisting of diethylene glycol, in a large amount. These effects enablethe resultant polyester polymer to exhibit a further improvedperformance such as, for example, thermal stability. Thetranseterification reaction is preferably carried out at a temperatureof 160 to 260° C.

In the present invention, where terephthalic acid is used as an aromaticdicarboxylic acid, the terephthalic acid and dimethyl terephthalate areemployed as starting materials for the polyester. In this case, arecycled dimethyl terephthalate obtained by depolymerizing apolyalkylene terephthalate or a recycled terephthalic acid obtained byhydrolyzing the recycled dimethyl terephthalate may be used. It isparticularly preferred to use, as the material source for preparation ofa polyester, recovered PET bottles, recovered polyester, fiber productsand recovered polyester film products, in view of effective utilizationof resources.

The polycondensation reaction may be carried out in a single rector orsuccessively conducted in a plurality of reactors. The polyester polymerproduced by the above-mentioned polycondensation procedure is usuallyextruded in a melt state into a filamentary form, and the filamentarymelt stream of the polyester polymer is cooled and then shaped (cut)into a chip form.

The polyester polymer obtained by the polycondensation procedure isoptionally further subjected to a solid phase polycondensationprocedure.

The solid phase polycondensation procedure is carried out at one or morestages, at a temperature of 190 to 230° C., under a pressure of 1 kPa to200 kPa, in an inert or unreactive gas atmosphere comprising, forexample, nitrogen, argon and/or carbon dioxide gas.

The polyester polymer produced by the above-mentioned solid phasepolycondensation procedure and in the form of chips is further treatedwith water by contacting water vapor-containing air with the polymer, todeactivate the catalyst contained in the polymer chips.

The procedure for producing the polyester polymer comprising theesterification step, and the polycondensation, step may be carried outin any one of batch, semi-continuous and continuous type procedures.

The polyester polymer usable for the present invention is preferablyselected from ployethylene terephthalate, polytrimethyleneterephthalate, and polytetramethylene terephthalate.

The polyester polymer usable for the present invention preferably has anL* value of 77 to 85 and a b* value of 2 to 5, determined in accordancewith the L*a*b* color specification of JIS Z 8729.

The polyester polymer produced by the above-mentioned procedures andusable for the present invention preferably has an intrinsic viscosityin the range of from 0.40 to 0.80, more preferably from 0.50 to 0.70. Ifthe intrinsic viscosity is less than 0.40, the resultant polyesterfibers may exhibit an insufficient mechanical strength. Also, if theintrinsic viscosity is more than 0.80, it may be necessary to design theintrinsic viscosity of the starting polyester polymer to be very high,and this may cause an economical disadvantage.

The polyester polymer usable for the present invention optionally asmall amount of an additive, for example, an antioxidant, an ultravioletray-absorber, a flame detardent, a fluorescent brightening agent, adulling agent, a color tone-controlling agent, a defoaming agent, anantistatic agent, antibacterial agents, a light stabilizer, a thermalstabilizer and a light-screening agent. Particularly, the polyesterpolymer is preferably added with titanium dioxide as a dulling agent andan antioxidant as a stabilizer.

The titanium dioxide is preferably in the form of particles having anaverage particle size of 0.01 to 2 μm and is preferably contained in acontent of 0.01 to 10% by mass in the polyester polymer.

In the case where the polyester polymer contains titanium dioxide as adulling agent and only the dulling agent consisting of titanium dioxideis removed from a sample of the polyester polymer to be subjected to ameasurement, the sample of the polyester polymer is dissolved inhexafluoroisopropanol, the solution is subjected to a centrifugalseparation testament to separate and precipitate the particles oftitanium dioxide from the solution, an upper clear liquid fraction ofthe solution is collected by a tilting method, and the solvent isevaporated away from the collected liquid fraction, to provide a polymersample to be subjected to the measurement.

The antioxidant preferably comprises a hindered phenolic antioxidant.The antioxidant is contained in a content of 1% by mass or less, morepreferably 0.005 to 0.5% by mass in the polyester polymer. If thecontent of the antioxidant is more than 1% by mass, the anti-oxidationeffect of the resultant resin may be saturated and too high a content ofthe antioxidant may cause scum to be generated in the polyester polymermelt during the melt spinning procedure. Also, the hindered phenolicantioxidant may be employed in a combination with a thioetherantioxidant against a secondary oxidation.

There is no limitation to the manner of mixing the antioxidant into thepolyester polymer. The mixing procedure may be carried out in any stagebetween the start of the transesterification reaction and the end of thepolycondensation reaction.

In the present invention, there is no limitation to the process forproducing the fibers from the polyester polymer, and the conventionalpolyester melt-spinning process can be used for the polyester fiber. Forexample, the above-mentioned polyester polymer is melted at atemperature in the range of from 270 to 300° C., and the melt is meltspun. In this melt-spinning procedure, the melt-spinning speed ispreferably 400 to 5000 m/min. When the melt-spinning procedure iscarried out at a speed in the above-mentioned range, the resultantfilaments may exhibit a sufficient mechanical strength and may bewound-up in a stable condition. The resultant undrawn polyesterfilaments are wound-up and then subjected to a drawing procedure or arecontinuously subjected to the drawing procedure without winding-up. Thepolyester fibers for the present invention may be subjected to amass-reduction treatment with an alkali, to improve the hand of thefilaments.

In the production of the polyester fibers, there is no limitation to theform of the spinneret. The spinning orifices may have a circular orirregular cross-sectional profiles, for example, a triangular or anotherpolygonal or flat cross-sectional profile and may be for hollow ornon-hollow filaments.

There is no limitation to the form of the polyester fibers usable forthe present invention. The polyester fiber for the present invention maybe in the form of continuous filaments or staple fibers. The polyesterfibers usable for the present invention may be in the form of twistedfiber yarns or non-twisted fiber yarns. Further, the polyester fibersusable for the present invention may be in the form of false-twisttextured fiber yarns, taslan-textured fiber yarns or fiber yarnsinterlaced by an interlacing method using air jet streams.

The total thickness, individual fiber thickness of the polyester fiberyarns for the present invention and the cover factor (CF) of the knittedor woven fabric of the present invention may be established in responseto the use thereof. The cover factor (CF) of the fabric is defined bythe following equation.CF=(DW _(p)/1.1)^(1/2×) MW _(p)+(DW _(f)/1.1)^(1/2) ×MW _(f)in which DW_(p) represents a total thickness in dtex of the warp yarnsof the fabric, MW_(p) represents a weave density in yarns/2.54 cm of thewarp yarns, DW_(f) represents a total thickness in dtex of the weftyarns and M_(f) represents a weave density in yarns/2.54 cm of the weftyarns.

For example, when the polyester fiber knitted or woven fabric of thepresent invention is prepared for clothes for gentlemen and ladies,clothes for sports and for uniforms, the polyester fiber yarns arepreferably designed to have a total thickness of 33 to 330 dtex, and anindividual fiber thickness of 0.4 to 10.0 dtex and the polyester fiberfabric is preferably designed to have a CF of 1000 to 3500. When thefabric is used for materials for interiors, the fiber yarns preferablyhave a total thickness of 22 to 1100 dtex and an individual fiberthickness of 0.4 to 22 dtex and the fabric preferably has a CF of 1000to 4500.

In the polyester fiber knitted or woven fabric of the present invention,the content of the polyester fibers is preferably 50% by mass or more,more preferably 60% by mass or more, still more preferably 100% by mass,based on the total mass of the knitted or woven fabric. In the polyesterfiber knitted or woven fabric of the present invention, the fiberscontained in addition to the polyester fibers are not limited tospecific types of fibers, as long as the additional fibers areappropriate to form the knitted or woven fabric. The additional fibersmay be at least one type of fibers selected from vegetable fibers, forexample, cotton and hemp fibers; animal hair fibers, for example, wool,Angora wool, cashmere, mohair, camel-hair and alpaca-hair; animalfibers, for example, silk, down and feather fibers; regenerated andsemisyntheitc fibers, for example, rayon and cellulose acetate fibers;and synthetic fibers, for example, nylon, aramide, polyvinyl alcohol,polyvinyl chloride, polyethylene terephthalate, polytrimethyleneterephthalate, polybutylene terephthalate, polyacrylate, polylacticacid, polyacrylonirile, polyethylene, polypropylene, polyurethane,polyphenylenesulfide, polyimide, polyacrylate, ethylene-vinyl alcoholcopolymer and polyetherester copolymer fibers.

In the polyester fiber knitted or woven fabric of the present invention,there is no limitation to the knitting and weaving structures, the wovenfabrics include known plain; twill and satin weaves.

The polyester fiber woven fabric of the present invention can beproduced by a conventional weaving method using the polyester fibers asspecified above. Also, polyester fiber woven fabric may be treated bythe known mass-reduction treatment with an alkali or the usual dyeingtreatment. Also, the polyester fiber woven fabric of the presentinvention may be treated by a conventional water-absorption,water-repellent, or raising treatment or with conventionalfunction-imparting agents, for example, an ultraviolet ray-screeningagent, an antistatic agent, a flame retardant agent, an antibacterialagent, a deodoring agent, a mothproofing agent, a light-regeneratingagent, a retroreflecting agent or an anionic ion-generating agent

The polyester fiber knitted fabrics of the present invention is notlimited to those having specific knitting structure and knittingdensity. To obtain a polyester fiber knitted fabrics having a good hand,the wale density is preferably 40 to 80 yarns/2.54 cm, more preferably50 to 70 yarns/2.54 cm, and the course density is preferably 30 to 70yarns/2.54 cm, more preferably 40 to 65 yarns/2.54 cm.

There is no limitation to the knitting structure of the polyester fiberknitted fabric of the present invention. The knitting structuresapplicable to the knitted fabric of the present invention include warpknitting structures and circular knitting structures. The tubularknitting structures include ponti romastich, Milano rib stitch, tuck ribstitch, Urakanoko stitch, single pique and double pique structures, thewarp knitting structures include single warp knitting structures, forexample, kalf, satin, backkalf, queens cord stitch, and sharkskin stitchstructures and double warp knitting structures, for example, doublerussel and double tricot structures.

The polyester fiber knitted fabrics of the present invention can beproduced from the polyester fiber yarns as mentioned above by aconventional knitting method. Also, the knitted fabric may be treated bya mass-reduction treatment with an alkali and/or a conventional dyeingprocedure. Also, the polyester fiber knitted fabric of the presentinvention is optionally further treated by a water-absorption,water-repellent and raising treatment or with a function-impartingagent, for example, an ultraviolet ray-screening agent, an antistaticagent, an antibacterial agent, a deodorizing agent, a mothproofingagent, a light-regenerating agent, a retroreflecting agent, and ananionic ion-generating agent.

EXAMPLES

The present invention will be further illustrated by the followingexamples which are not intended to restrict the scope of the presentinvention in any way.

In each of Examples 1 to 14 and Comparative Examples 1 to 8, intrinsicviscosity, color tone and metal content of an polyester polymer and theamount of foreign matter deposited and adhered around the spinneret inthe melt-spinning procedure (light of the foreign matter layer) aremeasured by the following measurements.

(1) Intrinsic Viscosity

An intrinsic viscosity (IV) of a polyester polymer was determined fromvalues of the viscosity of a solution of 0.6 g of the polyester polymerdissolved in 50 ml of orthochlorophenol at 35° C. measured at 35° C., byusing an Ostwald viscometer.

(2) Color Tone (L* Value and b* Value)

A polyester sample was melted at 290° C. under vacuum for 10 minutes andwas formed, on an aluminum plate, into a plate form having a thicknessof 3.0±1.0 mm. The resultant plate-shaped polyester test piece wasimmediately quenched in iced water, dried at 160° C. for one hour andthen subjected to a crystallization treatment. The resultantplate-shaped polyester test piece was placed on a white standard platefor regulating a color-difference meter and Hunter's L* value and b*value of the surface of the plate-shaped polyester test piece inaccordance with the L*a*b* color specification (JIS Z 8729) was measuredby a Hunter's color-difference meter CR-200 manufactured by Minolta Co.,Ltd. The L* value means the lightness and the lightness of the testpiece increases as the numerical value increases, while the b valuerepresents a yellowness and the yellowness of the test piece increasesas the b value increases.

(3) Metal Concentration Analysis

In the measurement of concentrations of titanium and phosphorus atoms inthe catalyst in the state of a solution, a sample of the catalystsolution was placed in a cell for a liquid.

When the catalyst is contained in a polyester polymer, a sample of thepolyester polymer containing the catalyst was heat-melted on an aluminumplate and a molded specimen having a flat surface was made by acompression press.

The catalyst solution sample or molded specimen was subjected to themetal concentration measurement by using a fluorescent X-ray analysisapparatus, Model 3270, manufactured by Rigaku Denki Kogyo K.K.

(4) Content of Diethylene Glycol (DEG)

A sample of the polyester polymer was decomposed with hydratedhydrazine, and the resultant decomposition product was subjected to agaschromatographic analysis using a gaschromatograph (model: 363-70,made by K.K. HITACHI SEISAKUSHO) to determine the content (mass %) ofdiethyleneglycol.

(5) Height of Foreign Matter Layer Deposited on Melt-Spinning Spinneret

After a polyester sample was formed into chips, the resultant chips weremelted at 290° C. and the melt was melt-spun by extruding through aspinning spinneret with 12 holes having a hole diameter of 0.15 mm at aextrusion rate of 600 m/min., for 2 days. The height of the layer of aforeign matter deposit formed on an outer periphery of the extrusionhole of the spinneret was measured. The larger the height of the layerof the deposit, the more a bending phenomenon of a filament-shapedstream of the extruded polyester melt occurs easily, resulting indecreased formability of the polyester. That is, the height of the layerof the deposit formed on the spinning spinneret is an index of theformability of the polyester.

(6) Tensile Strength and Ultimate Elongation of Fibers

The tensile strength and ultimate elongation of fibers were measured inaccordance with the procedure described in JIS L1013.

Example 1

A mixture of 100 parts by mass of dimethyl terephthalate with 70 partsby mass of ethylene glycol was further mixed with 0.009 part by weightof tetra-n-butyl titanate. The resultant mixture was placed in astainless steel reactor having heating means and pressurizing means, thepressure of the inside of the reactor was increased to 0.07 MPa and thetemperature of the mixture was increased into the range of from 140° C.to 240° C., to subject the mixture to a transesterification reaction.Then, the reaction mixture was further mixed with 0.04 part by mass oftriethyl phosphonoacetate, and the transesterification reaction wasended. The reaction mixture was moved to a polymerization reactor,heated to a temperature of 290° C., and subjected to a polycondensationreaction under a high vacuum of 26.67 Pa or less. A polyester polymerfree from dulling agent and having an intrinsic viscosity of 0.60 and adiethyleneglycol content of 1.5% by mass was obtained.

The resultant polyester polymer was formed into chips and dried byconventional procedures. The dried polymer chips were subjected to amelt-spinning procedure, to produce a undrawn multifilament yarn havinga yarn count of 333 dtex/36 filaments. The undrawn filament yarn wassubjected to a drawing procedure at a draw ratio of 4.0 to produce adrawn multifilament yarn having a yarn count of 83.25 dtex/30 filaments.The properties of the drawn multifilament yarn are shown in Table 1.

The drawn multifilament yarn was subjected to a circular knittingprocedure using a 28 gauge, 38 inch circular knitting machine, toproduce a knitted fabric with a smooth structure, a wale density of 52yarns/2.54 cm and a course density of 60 yarns/2.54 cm. In the knittingprocedure, the processability of the polyester multifilament yarn wasgood and it was judged that it was possible to maintain the processcondition stable over a long period of the process.

The resultant knitted grey fabric was dyed by using a high-pressuredyeing machine at a temperature of 130° C., the resultant dyed fabric inwetted condition was subjected to a padding procedure with a antistaticagent and then heat-set at a temperature of 165° C. in a heat-setter.The resultant finished knitted fabric had a smooth structure, a waledensity of 48 yarns/2.54 cm and a course density of 55 yarns/2.54 cm.

The resultant polyester fiber knitted fabric has a bursting strength of590 kPa, laundry dimensional changes of 0.3% in wale direction and 0.5%in course direction and was judged sufficiently usable for under-clothuse.

Referential Example 1

Synthesis of Titanium Trimellitate

A mixture was prepared by mixing titanium tetrabutoxide into a solutionof trimellitic anhydride in a concentration of 0.2% by mass inethyleneglycol in a molar ratio of titanium tetrabutoxide to trimelliticanhydride of ½:1. The mixture was kept in air at a temperature of 80° C.under the ambient atmospheric pressure for a time of 60 minutes to allowtitanium tetrabutoxide and trimellitic anhydride to react with eachother, and then the resultant reaction mixture was cooled to roomtemperature and then mixed into acetone in an amount of 10 times that ofthe reaction mixture, to allow the resultant catalytic reaction productto crystallize and precipitate. The resultant precipitate was separatedand collected from the reaction mixture by filtration through a filterpaper and dried at 100° C. for 2 hours.

The target reaction product of titanium tetrabutoxide with trimelliticanhydride, namely titanium trimellitate was obtained.

Example 2

Polyester fibers were produced by the same procedures as in Example 1except that as a titanium compound for a catalyst, the titaniumtrimellitate produced in Referential Example 1 was employed in an amountof 0.016 part. The measurement results are shown in Table 1.

The polyester multifilament yarn was subjected to a circular knittingprocedure using a 28 gauge, 38 inch circular knitting machine, toproduce a knitted fabric with a smooth structure, a wale density of 52yarns/2.54 cm and a course density of 60 yarns/2.54 cm. In the knittingprocedure, the processability of the polyester multifilament yarn wasgood and it was judged that it was possible to maintain the processcondition stable over a long period of the process.

The resultant knitted grey fabric was dyed by using a high pressuredyeing machine at a temperature of 130° C., the resultant dyed fabric inwetted condition was subjected to a padding procedure with a antistaticagent and then heat-set at a temperature of 165° C. in a heat-setter.The resultant finished knitted fabric had a smooth structure, a waledensity of 48 yarns/2.54 cm and a course density of 55 yarns/2.54 cm.

The resultant polyester fiber knitted fabric had a bursting strength of590 kPa, laundry dimensional changes of 0.3% in wale direction and 0.5%in course direction and was judged sufficiently usable for under-clothuse.

Examples 3 to 7

Polyester fibers were produced by the same procedures as in Example 1except that the titanium compound and the phosphorus compound as shownin Table 1 were used in the amounts as shown in Table 1, to provide acatalyst.

The measurement results are shown in Table 1.

The polyester multifilament yarn was subjected to a circular knittingprocedure using a 28 gauge, 38 inch circular knitting machine, toproduce a knitted fabric with a smooth structure, a wale density of 52yarns/2.54 cm and a course density of 60 yarns/2.54 cm. In the knittingprocedure, the processability of the polyester multifilament yarn wasgood and it was judged that it was possible to maintain the processcondition stable over a long period of the process.

The resultant knitted grey fabric was dyed by using a high pressuredyeing machine at a temperature of 130° C., the resultant dyed fabric inwetted condition was subjected to a padding procedure with a antistaticagent and then heat-set at a temperature of 165° C. in a heat-setter.The resultant finished knitted fabric had a smooth structure, a waledensity of 48 yarns/2.54 cm and a course density of 55 yarns/2.54 cm.

The resultant polyester fiber knitted fabric has a bursting strength of590 kPa, laundry dimensional changes of 0.3% in wale direction and 0.5%in course direction and was judged sufficiently usable for under-clothuse.

Comparative Examples 1 to 3

In each of Comparative Examples 1 to 3, polyester fibers were producedby the same procedures as in Example 1 except that the titanium compoundand the phosphorous compounds as shown in Table 1 were used in theamounts as shown in Table 1, to prepare a catalyst.

The measurement results are shown in Table 1.

The resultant polyester multifilament yarn was subjected to the knittingand dyeing procedure. In the knitting procedure, breakages of thepolyester multifilament yarn occurred and, in the dyeing procedure,scratch defects were generated on the fabric.

The resultant finished fabric had a plurality of scratch defects andexhibited unsatisfactory appearance and quality.

Comparative Example 4

A mixture of 100 parts by mass of dimethyl terephthalate with 70 partsby mass ethylene glycol was further mixed with 0.064 part by weight ofcalcium acetate hydrate. The resultant mixture was placed in a stainlesssteel reactor having heating means and pressurizing means, the presenceof the inside of the reactor was increased to 0.07 MPa and thetemperature of the mixture was increased into the range of from 140° C.to 240° C., to subject the mixture to a transesterification reaction.Then, the reaction mixture was further mixed with 0.044 part by mass ofan aqueous phosphoric acid solution having a concentration of 56% bymass, and the transesterification reaction was ended. The reactionmixture was placed in a polymerization reactor, mixed with antimonytrioxide in the amount as shown in heated up to a temperature of 290°C., and subjected to a polycondensation reaction under a high vacuum of26.67 Pa or less.

The resultant polyester polymer was formed into multifilaments in thesame procedures as in Example 1, and then into polyester fiber knittedfabric.

The measurement results are shown in Table 1.

The resultant polyester multifilament yarn was subjected to the knittingand dyeing procedures. In the knitting procedure, the polyestermultifilament yarn was frequently broken and in the dyeing procedure,scratch defects were generated on the fabric.

The resultant finished fabric had a plurality of rubbing defects andexhibited unsatisfactory appearance and quality. TABLE 1 Item Polyesterfibers Height Catalyst components Polyester polymer Ulti- of Sb Intrin-mate foreign Ti compound P compound compound sic Color Tensile elonga-matter Example Content Content (Sb₂O₃) M_(Ti) + M_(p) viscos- L* a*strength tion layer No Type (mmol %) Type (mmol %) (mmol %) M_(p)/M_(Ti)(mmol %) ity value value (cN/dtex) (%) (μm) Example 1 TBT 5 TEPA 30 — 635 0.620 79.0 3.0 3.7 27 3 2 TMT 5 TEPA 30 — 6 35 0.620 80.0 2.8 3.8 264 3 TMT 5 PEE 30 — 6 35 0.620 78.0 3.0 3.8 28 4 4 TMT 3 TEPA 15 — 5 180.600 80.0 2.3 3.6 27 2 5 TMT 7 TEPA 50 — 7 57 0.600 80.0 3.3 3.7 25 4 6TMT 5 TMP 30 — 6 35 0.600 77.0 4.0 3.6 26 3 7 Titanium 5 TEPA 30 — 6 350.600 78.0 4.5 3.6 29 4 acetate Compara- 1 TMT 5 TEPA 90 — 18 95 0.52083.0 0.0 3.2 22 4 tive 2 TMT 9 TEPA 100 — 11.1 109 0.600 78.0 3.0 3.7 294 Example 3 TMT 2 TEPA 7 — 3.5 9 0.600 80.0 2.0 3.6 27 3 4 — — — — 31 —— 0.620 78.0 3.0 3.9 28 50Notes for Table 1TBT: Titanium tetra-n-butoxideTMT: Titanium trimellitateTEPA: Triethyl phosphonoacetatePEE: Carboethoxymethane-diethyl phosphonate esterTHP: Trimethyl phosphate

Example 8

A polyester polymer was produced and, from the resultant polyesterpolymer, polyester multifilament yarns were produced by the sameprocedures as in Example 1.

The polyester multifilament yarns were employed in the form of anon-twisted yarn as warp and weft yarns to form a plain weave consistingof the above-mentioned polyester yarns only and having a warp density of97 yarns/2.54 cm and a weft density of 83 yarns/2.54 cm.

In the preparation step for the weaving procedure, the generation offluffs on the yarns in the warper is low and, in the weaving step,breakages of the warp yarns due to the generation of fluffs thereon andstoppages of weaving machine due to the insufficient reelability of theweft yarns were few and, thus, the weave-productivity of the yarns wasconfirmed to be excellent.

The resultant plain weave was subjected to the same dyeing, antistaticagent treatment and heat-setting procedures as in Example 1.

The resultant dyed and heat-set plain weave had a warp density of 109yarns/2.54 cm and a weft density of 94 yarns/2.54 cm and tear strengthsof 1.4N in the warp direction and 1.1N in the weft direction. Also, thelaundry dimensional changes of the plain weave were 1.3% in the warpdirection and 0.8% in the weft direction.

Example 9

A polyester polymer was produced and from the resultant polyesterpolymer, polyester multifilament yarns were produced by the sameprocedures as in Example 2.

The polyester multifilament yarns were employed in the form of anon-twisted yarn as warp and weft yarns to form a plain weave consistingof the above-mentioned polyester yarns only and having a warp density of97 yarns/2.54 cm and a weft density of 83 yarns/2.54 cm.

In the preparation step for weaving procedures, the generation of fluffson the yarn in the warper is low and, in the weaving step, breakages ofthe warp yarns due to generation of fluffs thereon and stoppages ofweaving machine due to the insufficient reelability of the weft yarnswere few and, thus, the weave-productivity of the yarns was confirmed tobe excellent.

Examples 10 to 14

In Examples 10 to 14, polyester polymers were respectively produced and,from the resultant polyester polymer, polyester multifilament yarns wereproduced by the same procedures as in Examples 3 to 7.

The polyester multifilament yarns were employed in the form of anon-twisted yarn as warp and weft yarns to form a plain weave consistingof the above-mentioned polyester yarns only and having a warp density of97 yarns/2.54 cm and a weft density of 83 yarns/2.54 cm.

In the preparation step for weaving procedures, the generation of fluffson the yarn in the warper is low and, in the weaving step, breakages ofthe warp yarns due to generation of fluffs thereon and stoppages ofweaving machine due to the insufficient reelability of the weft yarnswere few and, thus, the weave-productivity of the yarns was confirmed tobe excellent.

Comparative Examples 5 to 7

In Comparative Examples 5 to 7, polyester polymers were produced andpolyester multifilament yarns were produced from the polymers,respectively by the same procedures as in Comparative Examples 1 to 3.

Plain weaves were produced from the polyester multifilament yarns by thesame procedures as in Example 8, and the same dyeing procedures as inExample 8 were applied to the plain weaves.

In the preparation step of weaving procedures, the generation of fluffson the yarn in the warper occurred often. Also, in the weaving step, thebreakages of the warp yarns due to the generation of fluffs and thestoppages of the weaving machine due to insufficient reelability of theweft yarns occurred often. The productivity of weaves from the yarns wasinsufficient.

Comparative Example 8

In Comparative Example 8, a polyester polymer was produced and polyestermultifilament yarns were produced from the polymers, by the sameprocedures as in Comparative Example 4.

Plain weaves were produced from the polyester multifilament yarns by thesame procedures as in Example 8, and the same dyeing procedures as inExample 8 were applied to the plain weaves.

In the preparation step of weaving procedures, the generation of fluffson the yarn in the warper occurred often. Also, in the weaving step, thebreakages of the warp yarns due to the generation of fluffs and thestoppages of the weaving machine due to insufficient reelability of theweft yarns occurred often. The productivity of weaves from the yarnswere insufficient.

In Examples 15 to 22 and Comparative Examples 9 to 12 as illustratedbelow, the properties of polyester polymers and polyester fibers weredetermined by the measurements described below.

(1) Intrinsic Viscosity

An intrinsic viscosity (IV) of a polyester polymer was determined fromvalues of the viscosity of a solution of 0.6 g of the polyester polymerdissolved in 50 ml of orthochlorophenol at 35° C. measured at 35° C. byusing an Ostwald viscometer.

(2) Color Tone (L* Value and b* Value)

A polyester sample in the form of pellets was heat-treated andcrystallized in a dryer at a temperature of 160° C. for 90 minutes, thenan L* value and an a* value of the polyester sample in accordance withL*a*b* color specification (JIS Z 8729) was measured by using a colormachine, model: CM-7500, manufactured by Color Machine Co., Ltd.

(3) Metal Concentration Analysis

In the measurement of concentrations of titanium and phosphorus atoms inthe reaction product catalyst, a dried catalyst sample was mounted in ascanning electron microscope (Model S570, manufactured by HitachiInstruments Service Co., Ltd.) and the concentration of titanium andphosphorus atoms in the catalyst was determined by using an energydispersive X-ray microanalyzer (XMA, Model EMAX-7000, manufactured byHoriba Seisakusho, K.K.) connected to the scanning electron microscope.

In the measurement of the concentration of a residual catalytic metalsin the polyester, granular polyester samples were heat-melted on analuminum plate and a molded specimen having a flat surface was made by acompression press, and then the concentration of the metals in themolded specimen was determined by using a fluorescent X-ray analysisapparatus, Model 3270E, manufactured by Rigaku Denki Kogyo K.K.

(4) Tensile Strength and Ultimate Elongation of Fibers

The tensile strength and ultimate elongation of fibers were measured inaccordance with the procedure described in JIS L 1013.

(5) Amount of Foreign Matters Deposited on Spinning Spinneret

After a polyester sample was formed into chips, the resultant chips weremelted at 290° C. and the melt was melt-spun by extruding through aspinning spinneret with 12 holes having a hole diameter of 0.15 mm at aextrusion rate of 600 m/min., for 2 days. The height of the layer of adeposit formed on an outer periphery of the extrusion hole of thespinneret was measured. The larger the height of the layer of thedeposit, the more a bending phenomenon of a filament-shaped stream ofthe extruded polyester melt occurs easily, resulting in decreasedformability of the polyester. That is, the height of the layer of thedeposit formed on the spinning spinneret is an index of the formabilityof the polyester.

Example 15

Preparation of Titanium Compound:

In a 2 liter three-necked flask equipped with a means for mixing thecontents under stirring, 919 g of ethylene glycol and 10 g of aceticacid were charged and the mixture was stirred, and then 71 g of titaniumtetrabutoxide was gradually added to the mixture to thereby prepare atransparent solution of the titanium compound in ethylene glycol.Hereinafter, this solution will be referred to as a “TB solution”. Thetitanium concentration of this solution was measured by usingfluorescence X-ray. As a result, it was 1.02%.

Preparation of Phosphorus Compound:

In a 2 liter three-necked flask equipped with a means for mixingcontents under stirring with heating, 656 g of ethylene glycol wascharged, followed by heating to 100° C. with stirring. Upon arrival atthe target temperature, 34.5 g of monolauryl phosphate was added and themixture was dissolved by heating with stirring to obtain a transparentsolution. Hereinafter, this solution will be referred to as a “P1solution”.

Preparation of Catalyst:

The temperature of the P1 solution (about 690 g) was controlled to 100°C. with stirring and 310 g of the TB solution was gradually added to theP1 solution and, after the completion of the addition, the resultantreaction mixture was stirred at a temperature of 100° C. for one hour tocomplete the reaction between the titanium compound and the phosphoruscompound. The mixing ratio of the P1 solution to the TB solution wascontrolled so that the molar ratio of phosphorus atoms to titanium atomsbecomes 2.0:1.0. The resultant reaction product existed in the form of afine precipitate because the reaction product is insoluble in ethyleneglycol, and thus the reaction mixture was in the state of whiteturbidity. Hereinafter, this catalyst dispersion will be referred to asa “TP1-2.0 catalyst”.

To analyze the reaction precipitate in the TP1-2.0 catalyst, a portionof the reaction precipitate was used as a sample and the sample wasfiltered through a filter having a mesh opening size of 5 μm, thereby tocollect the reaction precipitate as a solid, and the precipitate waswashed with water and dried. The resulting reaction precipitate wassubjected to analysis of the element concentration using an XMAanalytical method. As a result, it contained 12.0% of titanium and 16.4%of phosphorus. The molar ratio of phosphorus atoms to titanium atoms was2.1:1.0. Furthermore, the reaction deposit was subjected to solid NMRanalysis. As a result, the following results were obtained. In themeasurement of C13 CP/MAS (frequency: 75.5 Hz), the disappearance ofpeaks at chemical shifts in 14 ppm, 20 ppm and 36 ppm derived from thebutoxide structure of titanium tetrabutoxide was observed. In themeasurement of P-31 DD/MAS frequency: 121.5 Hz), a new chemical shiftpeak 22 ppm, which has never before been present in monolaurylphosphate, was observed. It was clearly confirmed from these analyticalresults that the reaction precipitate obtained in this example containsa new product obtained by the reaction between the titanium compound andthe phosphorus compound.

In a reactor in which 225 parts by mass of an oligomer (namely anoligomer of terephthalate diester of ethyleneglycol) are contained, aslurry prepared by mixing 179 parts by mass of high purity terephthalicacid into 35 parts by mass of ethylene glycol was fed at a constantsupply rate in a nitrogen gas atmosphere at a temperature of 255° C.under the ambient atmospheric pressure, while stirring, and the slurrywas subjected to an esterification reaction, while distilling off waterand ethyleneglycol produced as by-products of the reaction. Four hoursafter the start of the esterification reaction, the reaction wascompleted. In this reaction, the degree of esterification was 98% andthe degree of polymerization of the produced oligomer was about 5 to 7.

The oligomer in an amount of 225 parts by mass, produced by theesterification reaction was placed in a polycondensation reactionvessel, and the above-mentioned TP1-2.0 catalyst in an amount of 3.34parts by mass were placed as a polycondensation catalyst in the reactionvessel. The reaction temperature of the reaction system contained in thereaction vessel was increased stepwise from 255° C. to 280° C. and atthe same time the reaction pressure of the reaction system was reducedstepwise from the ambient atmospheric pressure to 60 Pa to proceed thepolycondensation reaction while removing water and ethyleneglycolproduced, as by-products by the reaction, from the reaction system.

The proceeding degree of the polycondensation reaction was checked bymonitoring a load applied to the stirring wings in the reaction systemand the reaction was completed when the polymerization degree of theresulting polyester reaches a desired degree. The reaction mixture inthe vessel was continuously extruded through an extruding holes of thereaction vessel into a strand form, then the extruded reaction mixturestreams were solidified with cooling and then cut to prepare granularpellets having a granule size of about 3 mm.

The properties of the resultant polyethylene terephthalate are shown inTable 2.

The resultant polyester polymer chips were dried and then subjected to amelt-spinning procedure, to produce a undrawn multifilament yarn havinga yarn count of 333 dtex/36 filaments. The undrawn filament yarn wassubjected to a drawing procedure at a draw ratio of 4.0 to produce adrawn multifilament yarn having a yarn count of 83.25 dtex/36 filaments.The properties of the drawn multifilament yarn is shown in Table 2.

The drawn multifilament yarn was subjected to a circular knittingprocedure using a 28 gauge, 38 inch circular knitting machine, toproduce a knitted fabric with a smooth structure, a wale density of 52yarns/2.54 cm and a course density of 60 yarns/2.54 cm. In the knittingprocedure, the processability of the polyester multifilament yarn wasgood and it was judged that it was possible to maintain the processcondition stable over a long period of the process.

The resultant knitted grey fabric was dyed by using a high pressuredyeing machine at a temperature of 130° C., the resultant dyed fabric inwetted condition was subjected to a padding procedure with a antistaticagent and then heat-set at a temperature of 165° C. in a heat-setter.The resultant finished knitted fabric had a smooth structure, a waledensity of 48 yarns/2.54 cm and a course density of 55 yarns/2.54 cm.

The resultant polyester fiber knitted fabric had a bursting strength of590 kPa, laundry dimensional changes of 0.3% in wale direction and 0.5%in course direction and was judged sufficiently usable for under-clothuse.

Example 16

A polyester fiber knitted fabric was produced by the same procedures asin Example 15, except that monolauryl phosphate for the catalyst wasreplaced by monobutyl phosphate, and the amount of the monobutylphosphate and the process conditions for the preparation of the catalystwere changed to as described below.

Monobutyl phosphate in an amount of 28.3 g was dissolved in 537 g ofethylene glycol by heating. The resultant solution will be referred toas a P2 solution hereinafter. The P2 solution was mixed with 435 g ofthe TB solution to prepare a reaction product. The mixing ratio of theTB solution to the P2 solution was controlled to 2:1, in terms of molarratio of phosphate atoms to titanium atoms.

The resultant reaction product will be referred to as a TP2-2.0 catalysthereinafter.

In the preparation of the reaction product for the catalyst, thereaction temperature was 70° C. and the reaction time was one hour.

To analyze the TP2-2.0 catalyst, a sample of the reaction solution wasfiltered through a filter having a mesh opening size of 5 μm, thereby tocollect the reaction precipitate as a solid and the solid precipitatewas washed with water and dried. The element analysis of the reactionprecipitate was conducted in the same manner as in Example 15. As aresult, the content of titanium was 17.0% by mass, the content ofphosphorus was 21.2% by mass, and the molar ratio of phosphorus atoms totitanium atoms was 1.9:1.

The polyester polymer produced by using the catalyst was used for theproduction of a polyester multifilament yarn in the same procedures asin Example 15. The measurement results are shown in Table 2.

The polyester multifilament yarn was subjected to a circular knittingprocedure using a 28 gauge, 38 inch circular knitting machine, toproduce a knitted fabric a smooth structure, a wale density of 52yarns/2.54 cm and a course density of 60 yarns/2.54 cm. In the knittingprocedure, the processability of the polyester multifilament yarn wasgood and it was judged that it was possible to maintain the processcondition stable over a long period of the process.

The resultant knitted grey fabric was dyed by using a high pressuredyeing machine at a temperature of 130° C., the resultant dyed fabric inwetted condition was subjected to a padding procedure with a antistaticagent and then heat-set at a temperature of 165° C. in a heat-setter.The resultant finished knitted fabric had a smooth structure, a waledensity of 48 yarns/2.54 cm and a course density of 55 yarns/2.54 cm.

The resultant polyester fiber knitted fabric had a bursting strength of590 kPa, laundry dimensional changes of 0.3% in wale direction and 0.5%in course direction and was judged sufficiently usable for under-clothuse.

Example 17

A polyester fiber knitted fabric was produced by the same procedures asin Example 15, except that in the preparation of the catalyst, thepreparation amount of the TP1 solution and the addition amount of the TBsolution were changed to as described below.

Monolauryl phosphate in an amount of 31.3 g was dissolved in 594 g ofethylene glycol by heating. The resultant solution will be referred toas a B3 solution hereinafter. The P3 solution was mixed with 375 g ofthe TB solution to allow them to react with each other and to prepare areaction product. The mixing ratio of the TB solution to the B3 solutionwas controlled to 1.5:1, in terms of molar ratio of phosphate atoms totitanium atoms.

The resultant reaction product will be referred to as a TP3-1.5 catalysthereinafter.

The polyester polymer produced by using the catalyst was used for theproduction of a polyester multifilament yarn in the same procedures asin Example 15. The measurement results are shown in Table 2.

The polyester multifilament yarn was subjected to a circular knittingprocedure using a 28 gauge, 38 inch circular knitting machine, toproduce a knitted fabric a smooth structure, a wale density of 52yarns/2.54 cm and a course density of 60 yarns/2.54 cm. In the knittingprocedure, the processability of the polyester multifilament yarn wasgood and it was judged that it was possible to maintain the processcondition stable over a long period of the process.

The resultant knitted grey fabric was dyed by using a high pressuredyeing machine at a temperature of 130° C., the resultant dyed fabric inwetted condition was subjected to a padding procedure with a antistaticagent and then heat-set at a temperature of 165° C. in a heat-setter.The resultant finished knitted fabric had a smooth structure, a waledensity of 48 yarns/2.54 cm and a course density of 55 yarns/2.54 cm.

The resultant polyester fiber knitted fabric had a bursting strength of590 kPa, laundry dimensional changes of 0.3% in wale direction and 0.5%in course direction and was judged sufficiently usable for under-clothuse.

Example 18

A polyester fiber knitted fabric was produced by the same procedures asin Example 16, except that the preparation amount of the TP2 solutionand the addition amount of the TB solution were changed to as shownbelow.

Monobutyl phosphate in an amount of 30.0 g was dissolved in 627 g ofethylene glycol by heating. The resultant solution will be referred toas a P4 solution hereinafter. The P4 solution was mixed with 340 g ofthe TB solution to allow them to react with each other and to prepare areaction product. The mixing ratio of the TB solution to the P4 solutionwas controlled to 3.0:1, in terms of molar ratio of phosphate atoms totitanium atoms.

The resultant reaction product will be referred to as a TP4-3.0 catalysthereinafter.

The polyester polymer produced by using the catalyst was used for theproduction of a polyester multifilament yarn in the same procedures asin Example 15. The measurement results are shown in Table 2.

The polyester multifilament yarn was subjected to a circular knittingprocedure using a 28 gauge, 38 inch circular knitting machine, toproduce a knitted fabric a smooth structure, a wale density of 52yarns/2.54 cm and a course density of 60 yarns/2.54 cm. In the knittingprocedure, the processability of the polyester multifilament yarn wasgood and it was judged that it was possible to maintain the processcondition stable over a long period of the process.

The resultant knitted grey fabric was dyed by using a high pressuredyeing machine at a temperature of 130° C., the resultant dyed fabric inwetted condition was subjected to a padding procedure with a antistaticagent and then heat-set at a temperature of 165° C. in a heat-setter.The resultant finished knitted fabric had a smooth structure, a waledensity of 48 yarns/2.54 cm and a course density of 55 yarns/2.54 cm.

The resultant polyester fiber knitted fabric has a bursting strength of590 kPa, laundry dimensional changes of 0.3% in wale direction and 0.5%in course direction and was judged sufficiently usable for under-clothuse.

Comparative Example 9

A polyester multifilament yarn was produced by the same procedures as inExample 15, except that as a polycondensation catalyst, a solution of1.3% by mass of antimony trioxide in ethyleneglycol was employed in anamount of 4.83 parts by mass, and the antimony trioxide solution furthercomprised 0.121 part by mass of a solution of 25% by mass of trimethylphosphate in ethylene glycol. The measurement results are shown in Table2. The polyester multifilament yarn was subjected to the knitting anddyeing procedures in the same manner as in Example 15.

In the knitting procedure, the breakages of the yarns occurred often andin the dyeing procedure, scratch defects were often generated on thefabric. Thus the resultant finished fabric exhibited unsatisfactoryappearance and quality.

Comparative Example 10

A polyester multifilament yarn was produced by the same procedures as inExample 15, except that as a polycondensation catalyst, the TB solutionprepared in Example 15 was employed alone in an amount of 1.03 parts bymass. The polycondensation time was changed to 95 minutes. Themeasurement results are shown in Table 2.

The polyester multifilament yarn was subjected to the knitting anddyeing procedures in the same manner as in Example 15. In the knittingprocedures, the breakages of the yarns occurred and in the dyeingprocedure, the scratch defects were generated on the fabric. Thus, theresultant finished knitted fabric exhibited unsatisfactory appearanceand quality.

Comparative Example 11

A polyester multifilament yarn was produced by the same procedures as inExample 15, except that, as a polycondensation catalyst, the TB solutionand the P1 solution were separately mixed in amounts of 1.03 parts bymass of the TB solution and 2.30 parts by mass of the P1 solution intothe polycondensation reaction system for producing the polyesterpolymer, without reacting the TB solution with the P1 solution. Themeasurement results are shown in Table 2.

The polyester multifilament yarn was subjected to the knitting anddyeing procedures in the same manner as in Example 15. In the knittingprocedures, breakages of the yarns occurred and in the dyeing procedure,scratch defects were generated on the fabric. Thus, the resultantfinished knitted fabric exhibited unsatisfactory appearance and quality.

Comparative Example 12

A polyester multifilament yarn was produced by the same procedures as inExample 16, except that, as a polycondensation catalyst, the TB solutionand the P2 solution were separately mixed in amounts of 1.03 parts bymass of the TB solution and 2.3 parts by mass of the P2 solution intothe polycondensation reaction system for producing the polyesterpolymer, without reacting the TB solution with the P2 solution.

The measurement results are shown in Table 2.

The polyester multifilament yarn was subjected to the knitting anddyeing procedures in the same manner as in Example 15. In the knittingprocedure, breakages of the yarns occurred and, in the dyeing procedure,scratch defects were generated on the fabric. Thus, the resultantfinished knitted fabric exhibited unsatisfactory appearance and quality.TABLE 2 Item Polyester fiber Catalyst Height of Molar foreign ratio ofPolyester polymer Ultimate matter layer Content of P atoms Color Tensileelonga- formed around Type of catalyst to Ti Intrinsic L* value/strength tion spinneret Example No catalyst Ti (ppm)/P (ppm) atomsviscosity b* value (cN/dtex) (%) (μm) Example 15 TP1-2.0 52/64 2.0:10.64 81/2.0 3.8 25 4 16 TP2-2.0 48/60 2.0:1 0.64 81/2.2 3.7 23 5 17TP3-1.5 32/28 1.5:1 0.64 81/3.0 3.7 22 4 18 TP4-3.0 152/260 3.0:1 0.6481/2.4 3.8 23 7 Comparative 9 Sb₂O₃ 250 (Sb) — 0.64 75/2.5 3.7 24 32Example 10 TB 52/0  — 0.64 81/8.0 3.8 24 9 solution 11 TB + P1 52/56 —0.64 81/7.6 3.6 25 9 solutions 12 TB + P2 52/56 — 0.64 81/7.9 3.5 26 8solutions

Example 19

By the same procedures as in Example 15, a polyester polymer wasproduced and polyester multifilament yarns were produced from thepolyester polymer.

The multifilament yarns in the form of a non-twisted yarn were employedas warp and weft yarns to produce a plain weave consisting of thepolyester multifilament yarns only, and having a warp density of 97yarns/2.54 cm and a weft density of 83 yarns/2.54 cm.

In the preparation step for the weaving procedures, the generation offluffs on the yarn in the warper is low, and in the weaving step,breakages of the warp yarns due to generation of the fluffs on the yarnsand stoppings of weaving machine due to the insufficient reelability ofthe weft yarns were few, and thus the weave-productivity of the yarnswas excellent.

The resultant plain weave was dyed, treated with an antistatic agent andheat-set by the same procedures as in Example 15.

The resultant weave had a warp density of 109 yarns/2.54 cm and a weftdensity of 94 yarns/2.54 cm and exhibited tear strengths of 1.4N in thewarp direction and 1.1N in the weft direction and a laundry dimensionalchanges of 1.3% in the warp direction and 0.8% in the weft direction.

Example 20

By the same procedures as in Example 16, a polyester polymer wasproduced and polyester multifilament yarns were produced from thepolyester polymer.

The multifilament yarns in the form of a non-twisted yarn were employedas warp and weft yarns to produce a plain weave consisting of thepolyester multifilament yarns only, and having a warp density of 97yarns/2.54 cm and a weft density of 83 yarns/2.54 cm.

In the preparation step for the weaving procedures, the generation offluffs on the yarns in the warper is few, and in the weaving step,breakages of the warp yarns due to generation of fluffs on the yarns andstoppings of weaving machine due to the insufficient reelability of theweft yarns were few, and thus the weave-productivity of the yarns wasexcellent.

Example 21

By the same procedures as in Example 17, a polyester polymer wasproduced and polyester multifilament yarns were produced from thepolyester polymer.

The multifilament yarns in the form of a non-twisted yarn were employedas warp and weft yarns to produce a plain weave consisting of thepolyester multifilament yarns only, and having a warp density of 97yarns/2.54 cm and a weft density of 83 yarns/2.54 cm.

In the preparation step for the weaving procedures, the generation offluffs on the yarn in the warper is low, and in the weaving step,breakages of the warp yarns due to generation of fluffs on the yarns andstoppings of weaving machine due to the insufficient reelability of theweft yarns were few, and thus the weave-productivity of the yarns wasexcellent.

Example 22

By the same procedures as in Example 18, a polyester polymer wasproduced and polyester multifilament yarns were produced from thepolyester polymer.

The multifilament yarns in the form of a non-twisted yarn were employedas warp and weft yarns to produce a plain weave consisting of thepolyester multifilament yarns only, and having a warp density of 97yarns/2.54 cm and a weft density of 83 yarns/2.54 cm.

In the preparation step for the weaving procedures, the generation offluffs on the yarn in the warper is low, and in the weaving step,breakages of the warp yarns due to generation of fluffs on the yarns andstoppings of weaving machine due to the insufficient reelability of theweft yarns were few, and thus the weave-productivity of the yarns wasexcellent.

Comparative Example 13

By the same procedures as in Comparative Example 9, a polyester polymerwas produced and polyester multifilament yarns were produced from thepolyester polymer.

The polyester multifilament yarns were subjected to the same weaving anddyeing procedures as in Example 19.

In the preparation step for the weaving procedures, a large number offluffs were formed on the yarns in the warper, and in the weaving step,breakages of the warp yarns due to generation of the fluffs on the yarnsand stoppings of weaving machine due to the insufficient reelability ofthe weft yarns occurred frequently, and thus the weave-productivity ofthe yarns was insufficient.

Comparative Example 14

By the same procedures as in Comparative Example 10, a polyester polymerwas produced and polyester multifilament yarns were produced from thepolyester polymer.

The polyester multifilament yarns were subjected to the same weaving anddyeing procedures as in Example 19.

In the preparation step for the weaving procedures, a large number offluffs were formed on the yarns in the warper, and in the weaving step,breakages of the warp yarns due to the generation of the fluffs on theyarns and stoppings of weaving machine due to the insufficientreelability of the weft yarns frequently occurred, and thus theweave-productivity of the yarns was poor.

Comparative Example 15

By the same procedures as in Comparative Example 11, a polyester polymerwas produced and polyester multifilament yarns were produced from thepolyester polymer.

The polyester multifilament yarns were woven and dyed in same manner asin Example 19.

In the preparation step for the weaving procedures, a large number offluffs were formed on the yarns in the warper, and in the weaving step,breakages of the warp yarns due to generation of the fluffs on the yarnsand stoppings of weaving machine due to the insufficient reelability ofthe weft yarns frequently occurred, and thus the weave-productivity ofthe yarns was insufficient.

Comparative Example 16

By the same procedures as in Comparative Example 12, a polyester polymerwas produced and polyester multifilament yarns were produced from thepolyester polymer.

The polyester multifilament yarns were woven and dyed in same manner asin Example 19.

In the preparation step for the weaving procedures, a large number offluffs were generated on the yarns in the warper, and in the weavingstep, breakages of the warp yarns due to generation of the fluffs on theyarns and stoppings of weaving machine due to the insufficientreelability of the weft yarns frequently occurred, and thus theweave-productivity of the yarns was insufficient.

1. A polyester fiber knitted or woven fabric formed from yarns comprising polyester fibers comprising, as a principal component, a polyester polymer which has been produced by polycondensing an aromatic dicarboxylate ester in the presence of a catalyst, wherein the catalyst comprises at least one member selected from mixtures (1) and reaction products (2); (1) the mixtures (1) for the catalyst comprises a titanium compound component (A) mixed with phosphorus compound component (B), in which mixtures (1), the component (A) comprises at least one member selected from the group consisting of (a) titanium alkoxides represented by the general formula (I):

in which formula (i), R¹, R², R³ and R⁴ respectively and independently from each other represent a member selected from alkyl groups having 1 to 20 carbon atoms and a phenyl group, m represent an integer of 1 to 4, and when m represents an integer of 2, 3 or 4, the 2, 3 or 4 R²s and R³s may be respectively the same as each other or different from each other, and (b) reaction products of the titanium compounds of the general formula (i) with aromatic polycarboxylic acids represented by the formula (ii):

in which formula (II), n represents an integer of 2 to 4, or anhydrides of the acids of the formula (II); and the component (B) comprising at least one phosphorus compound represented by the general formula (III):

in which formula (III), R⁵, R⁶ and R⁷ respectively and independently from each other represent an alkyl group having 1 to 4 carbon atoms, X represents a member selected from a —CH₂— group and a —CH(Y)— group (wherein Y represents a phenyl group), the mixture (1) for the catalyst for the polycondensation being employed in an amount satisfying the requirements represented by the following expressions of relation (i) and (ii): 1≦M _(p) /M _(Ti)≦15  (i) and 10≦M _(p) +M _(Ti)≦100  (ii) wherein M_(Ti) represents a ratio in % of a value in milli mole of titanium element contained in the titanium compound component (A) to a value in mole of the aromatic dicarboxylate ester, and M_(p) represents a ratio in % of a value in milli mole of phosphorus element contained in the phosphorus compound component (A) to the value in mole of the aromatic dicarboxylate ester, (2) the reaction products (2) for the catalyst comprises a component (C) reacted with a component (D), in which reaction products (2), the component (C) comprises at least one member selected from the group consisting of (C) titanium alkoxides represented by the general formula (IV):

in which formula (IV), R¹, R⁹, R¹⁰ and R¹¹ respectively and independently from each other represents an alkyl group having 1 to 20 carbon atoms, p represents an integer of 1 to 3, and when p represents an integer of 2 or 3, 2 or 3 R⁹s and R¹⁰s may be respectively the same as each other or different from each other, and (d) reaction products of the titanium alkoxides of the general formula (IV) with aromatic polycarboxylic acids represented by the above-mentioned general formula (II) or anhydrode of the acids; and the component (D) comprises at least one phosphorus compound represented by the general formula (V):

in which formula (V), R¹² represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and q represents an integer of 1 or
 2. 2. The polyester fiber knitted or woven fabric as claimed in claim 1, wherein in each of the component (A) of the mixture (1) and the component (C) of the reaction products (2) for the catalyst, a reaction molar ratio of each of titanium alkoxides (a) and (c) to the aromatic polycarboxylic acid of the general formula (II) or the anhydride thereof is in the range of from 2:1 to 2:5.
 3. The polyester fiber knitted or woven fabric as claimed in claim 1, wherein in the reaction product (2) for the catalyst, a reaction amount ratio of the component (D) to the component (C) is in the range of, in terms of ratio (P/Ti) of the molar amount of phosphorus atoms contained in the component (D) to the molar amount of titanium atoms contained in the component (C), from 1:1 to 3:1.
 4. The polyester fiber knitted or woven fabric as claimed in claim 1, wherein the phosphorus compound of the general formula (V) for the reaction product (2) is selected from monoalkyl phosphates.
 5. The polyester fiber knitted or woven fabric as claimed in claim 1, wherein the dialkyl aromatic dicarboxylate ester is one produced by a transesterification reaction of a dialkyl ester of an aromatic dicarboxylic acid with an alkylene glycol.
 6. The polyester fiber knitted or woven fabric as claimed in claim 5, wherein the aromatic dicarboxylic acid is selected from terephthalic acid, 1,2-naphthalene dicarboxylic acid, phthalic acid, isophthalic acid, diphenyldicarboxylic acid, and diphenoxyethane dicarboxylic acid and the alkylene glycol is selected from ethylene glycol, butylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol and dodecamethylene glycol.
 7. The polyester fiber knitted or woven fabric as claimed in claim 1, wherein the polyester polymer has an L* value of 77 to 85 and a b* value of 2 to 5, determined in accordance with the L*a*b* color specification of JIS Z
 8729. 